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Defect Engineering in Large-Scale CVD-Grown Hexagonal Boron Nitride: Formation, Spectroscopy, and Spin Relaxation Dynamics (Small 8/2026) 大规模CVD生长六方氮化硼的缺陷工程:形成、光谱和自旋松弛动力学(Small 8/2026)
IF 12.1 2区 材料科学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2026-02-06 DOI: 10.1002/smll.72117
Ivan V. Vlassiouk, Yueh-Chun Wu, Alexander Puretzky, Liangbo Liang, John Lasseter, Bogdan Dryzhakov, Ian Gallagher, Sujoy Ghosh, Nickolay Lavrik, Ondrej Dyck, Andrew R. Lupini, Marti Checa, Liam Collins, Harry M. Meyer III, Huan Zhao, Farzana Likhi, Kai Xiao, Ilia Ivanov, David Glasgow, Alexander Tselev, Benjamin Lawrie, Sergei Smirnov, Steven J. Randolph

Defect Engineering

Optically active defects in hexagonal boron nitride have become a versatile platform for advancing quantum technologies. Defect formation in this 2D material depends on the energy and type of bombarding particles and their interactions with underlying substrates. Suspended samples enable more controlled defect engineering, demonstrated on large-scale CVD films. More in article number e06874, Ivan V. Vlassiouk and co-workers.

六方氮化硼的光学活性缺陷已成为推进量子技术的通用平台。这种二维材料的缺陷形成取决于轰击粒子的能量和类型以及它们与底层衬底的相互作用。悬浮样品可以实现更可控的缺陷工程,这在大规模CVD薄膜上得到了证明。更多文章编号e06874, Ivan V. Vlassiouk和同事。
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引用次数: 0
Printable Potentiometric Ion-Selective Electrodes Based on Carbon Fiber and Ti3C2Tx MXene Nanoflakes: Eliminating Complex Modifications (Small 8/2026) 基于碳纤维和Ti3C2Tx MXene纳米薄片的可打印电位离子选择电极:消除复杂修饰(Small 8/2026)
IF 12.1 2区 材料科学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2026-02-06 DOI: 10.1002/smll.72574
Ilya Korolev, Anna Bondar, Arina Pavlova, Ksenia Maleeva, Valentina Minisheva, Grigory Ovinov, Ekateriva V. Skorb, Evgeny Smirnov

Portable Sensors

In article number e10942, Evgeny Smirnov and co-workers explore the performance of MXene-based ion-selective electrodes (ISEs) for portable environmental and healthcare monitoring. It compares carbon fibre-based ISEs (CF ISEs) with MXene-modified versions, highlighting MXene potential for enhancing sensitivity, printability, and cost-effectiveness in ion detection. The findings show that MXene based electrodes offer promising advantages for flexible and miniaturized sensing systems.

便携式传感器
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引用次数: 0
Short-Range-Engineered Nd-Doped IrOx Enables Oxide Path Mechanism for High-Performance PEM Water Electrolysis 短程工程nd掺杂IrOx实现高性能PEM水电解的氧化物路径机制
IF 13.3 2区 材料科学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2026-02-06 DOI: 10.1002/smll.202511956
Guangyue Liu, Lifang Chen, Zhenyu Liu, Jingchao Chen, Ruimin Ding, Xi Yin
Proton-exchange-membrane water electrolysis (PEMWE) demands high-performance anodes with minimal iridium content, yet conventional Ir-based catalysts suffer from an inherent activity-stability trade-off. We address this challenge by designing neodymium-doped amorphous IrOx catalysts (Nd-IrOx) that enable precise control over short-range structure to activate the oxide path mechanism (OPM). Incorporating Nd3+ into an amorphous IrOx matrix dominated by edge-sharing [IrO6] octahedra optimizes the prerequisites for the OPM: lattice distortion tailors Ir-Ir distances to enable direct *O-O* coupling, while electronic modulation stabilizes OH ligands within the local coordination environment, facilitating *O formation. The optimized Nd-IrOx catalyst delivers an ultralow acidic OER overpotential of 254 mV at 10 mA cm−2 with 520 h of stability. Remarkably, PEMWE employing an ultralow Ir-loading anode (0.5 mgIr cm−2) achieves a DOE-relevant current density (4 A cm−2 at 1.9 V) and remarkable 1000-h stability at 1 A cm−2. This work pioneers short-range engineering in Ir-based oxides, offering fundamental insights for catalyst design and OER pathway control toward efficient hydrogen production.
质子交换膜水电解(PEMWE)需要高性能的阳极和最少的铱含量,然而传统的ir基催化剂存在固有的活性-稳定性权衡。我们通过设计掺钕非晶IrOx催化剂(Nd-IrOx)来解决这一挑战,该催化剂能够精确控制短程结构以激活氧化物路径机制(OPM)。将Nd3+加入到由边共享[IrO6]八面体主导的非晶态IrOx矩阵中,优化了OPM的先决条件:晶格畸变调整了Ir-Ir距离,使*O-O*直接耦合,而电子调制稳定了局部配位环境中的OH配体,促进了*O的形成。优化后的Nd-IrOx催化剂在10 mA cm - 2下提供了254 mV的超低酸性OER过电位,稳定性为520 h。值得注意的是,采用超低负载ir阳极(0.5 mgIr cm - 2)的PEMWE实现了与doe相关的电流密度(1.9 V时为4 a cm - 2)和在1 a cm - 2时的1000 h稳定性。这项工作开创了基于ir的氧化物的短程工程,为催化剂设计和OER路径控制提供了基本的见解,以实现高效的氢气生产。
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引用次数: 0
Genetically Encoded Sterol-Modification of a Synthetic Intrinsically Disordered Protein Drives Its Self-Assembly Into Diverse Morphologies 合成的内在无序蛋白的遗传编码甾醇修饰驱动其自组装成不同的形态
IF 13.3 2区 材料科学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2026-02-06 DOI: 10.1002/smll.202509658
Sarah Yeon-Kyoung Kim, Taranpreet Kaur, Yulia Shmidov, Matthew Yiren Wang, Lixin Fan, Abigail Leo, Nicolas Angustia, Yan Xiang, Daniel Reker, Ashutosh Chilkoti
Post-translational modifications (PTMs) of proteins are used by natural systems to expand beyond the 20 canonical amino acids. The variation introduced at the sequence level by PTMs after expression leads to changes in both the structure and function of proteins. PTMs expand the chemical repertoire from which new biomaterials can be constructed. Inspired by the post-translational conjugation of cholesterol to proteins, we have synthesized five new hybrid lipid-protein biomaterials called Sterol-modified polypeptides (STaMPs). These STaMPs consist of an elastin-like polypeptide (ELP) conjugated to a sterol, namely coprostanol, epicoprostanol, androstanol, galeterone, or dehydroepiandrosterone. We show that STaMPs exhibit sterol-dependent self-assembly behavior, ranging from predominantly monomeric random coils for the most hydrophilic sterols to spherical micelles for the most hydrophobic sterols. Furthermore, the sterols modify the typical LCST behavior of ELPs in a predictable fashion depending on the hydrophobicity of the sterol appended.
蛋白质的翻译后修饰(PTMs)被自然系统用于扩展超过20个典型氨基酸。ptm在表达后在序列水平上引入的变异导致了蛋白质结构和功能的改变。PTMs扩展了构建新生物材料的化学库。受翻译后胆固醇与蛋白质结合的启发,我们合成了五种新的脂蛋白杂交生物材料,称为甾醇修饰多肽(STaMPs)。这些邮票由弹性蛋白样多肽(ELP)偶联到固醇,即coprostanol,表prostanol,雄甾醇,galeterone,或脱氢表雄酮。研究表明,stamp具有依赖于甾醇的自组装行为,从最亲水的甾醇的主要单体随机线圈到最疏水的甾醇的球形胶束。此外,根据附加的甾醇的疏水性,甾醇以一种可预测的方式改变了elp的典型LCST行为。
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引用次数: 0
High Thermoelectric Performance Achieved in Nb0.8Ti0.2FeSb via PbI2-Driven Multiscale Defect Engineering 通过pbi2驱动的多尺度缺陷工程实现Nb0.8Ti0.2FeSb的高热电性能
IF 13.3 2区 材料科学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2026-02-06 DOI: 10.1002/smll.72751
Panpan Peng, Zhihao Li, Jianhong Hu, Amensisa Negasa Begi, Peng Cao, Fulong Liu, Tingting Chen, Chunlei Wang, Hongchao Wang
NbFeSb-based half-Heusler alloys offer high electrical conductivity and mechanical strength, yet suffer from high lattice thermal conductivity. Constructing complex microstructures to reduce thermal conductivity remains challenging due to high-temperature processing. This study introduces PbI2 during ball-milling, which sublimates during sintering, creating a hierarchical structure in Nb0.8Ti0.2FeSb. The resulting features—PbI2 nanophases, core–shell pore@Pb structures, multiscale porosity, and Fe vacancies—enable full-spectrum phonon scattering. Furthermore, the presence of Fe vacancies softens the lattice and reduces the sound velocity. Together, these reduce lattice thermal conductivity to 3.34 W m−1 K−1 at 973 K, a 32% decrease. Lowered grain-boundary barriers reduce hole trapping, increasing carrier concentration and electrical conductivity, leading to a power factor of 52.7 µW cm−1 K−2 and zT ~ 1. The material maintains high compressive strength (1132 MPa, 38% improvement) and microhardness (950 HV), as second-phase strengthening offsets pore-induced weakening. This approach demonstrates that sublimable compounds can form full-scale hierarchical architectures in high-temperature thermoelectrics, enabling both robust mechanical and thermoelectric performance.
基于nbbfsb的半赫斯勒合金具有高导电性和机械强度,但晶格导热系数高。由于高温加工,构建复杂的微结构来降低导热系数仍然是一个挑战。本研究在球磨过程中引入PbI2,在烧结过程中升华,形成Nb0.8Ti0.2FeSb的分层结构。由此产生的特征- pbi2纳米相,核壳pore@Pb结构,多尺度孔隙率和铁空位-使全谱声子散射成为可能。此外,铁空位的存在软化了晶格,降低了声速。在973 K时,晶格热导率降低到3.34 W m−1 K−1,降低了32%。降低晶界屏障减少空穴捕获,增加载流子浓度和电导率,导致功率因数为52.7 μ W cm−1 K−2和zT ~ 1。由于第二阶段强化抵消了孔隙引起的弱化,该材料保持了较高的抗压强度(1132 MPa,提高38%)和显微硬度(950 HV)。这种方法表明,可升华化合物可以在高温热电材料中形成全尺寸的分层结构,从而实现强大的机械和热电性能。
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引用次数: 0
Unveiling a Tetrahedrally Coordinated Cobalt-Nucleotide Hydrogel as an Efficient Bifunctional Electrocatalyst for Alkaline Water Electrolysis 揭示了一种四面体配位钴核苷酸水凝胶作为碱水电解的高效双功能电催化剂
IF 13.3 2区 材料科学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2026-02-06 DOI: 10.1002/smll.202512303
Vidhi Agarwal, Bidyut Chutia, Ravindra Vishwakarma, Aditya Prasun, Amrita Chakraborty, Sasanka Deka, Tridib K Sarma
Amid the global drive to eliminate carbon emissions and to mitigate the energy crisis, water splitting emerges as a beacon of innovation, converting water into clean hydrogen and oxygen. Most electrocatalysts for water splitting rely on precious metals, highlighting the demand for cost-effective, efficient, and reproducible alternatives. Herein, we report the development of a cobalt-adenosine monophosphate (CAH) hydrogel as a bifunctional catalyst for overall water splitting in alkaline conditions with a cell voltage of 1.56 V at 10 mA cm−2, outperforming the benchmark catalytic system IrO2||Pt/C (1.62 V at 10 mA cm−2). Three crucial factors contributed to the notable water splitting of this hydrogel: (i) phosphate group in the AMP coordinated with central Co2+ ions, promoting effective adsorption of key intermediates, (ii) tetrahedral arrangement around cobalt atoms making the active site more exposed and accessible, enabling better interaction with reactants and intermediates, (iii) the formation of hydrogel enhances electrolyte confinement, thus accelerating reaction kinetics. At elevated temperature, the hydrogel achieves a low cell voltage of 1.42 V at 1.0 M KOH. Even under industrially relevant harsh conditions, the hydrogel achieves 10 mA cm−2 at 1.53 V, underscoring its durability. This simple nucleotide-based coordination polymer might bring significant advancement in sustainable energy conversion.
在全球消除碳排放和缓解能源危机的努力中,水分解成为创新的灯塔,将水转化为清洁的氢和氧。大多数用于水分解的电催化剂都依赖于贵金属,这突出了对成本效益高、效率高、可再生替代品的需求。在此,我们报告了一种钴-磷酸腺苷(CAH)水凝胶作为双功能催化剂在碱性条件下的整体水分解,电池电压为1.56 V, 10 mA cm - 2,优于基准催化体系IrO2||Pt/C (1.62 V, 10 mA cm - 2)。三个关键因素促成了该水凝胶的显著水分裂:(1)AMP中的磷酸基团与中心Co2+离子配合,促进了关键中间体的有效吸附;(2)钴原子周围的四面体排列使活性位点更暴露和可接近,从而更好地与反应物和中间体相互作用;(3)水凝胶的形成增强了电解质约束,从而加速了反应动力学。在高温下,水凝胶在1.0 M KOH下达到1.42 V的低电池电压。即使在工业相关的恶劣条件下,水凝胶在1.53 V下也能达到10 mA cm - 2,强调了其耐用性。这种简单的核苷酸基配位聚合物可能在可持续能量转换方面取得重大进展。
{"title":"Unveiling a Tetrahedrally Coordinated Cobalt-Nucleotide Hydrogel as an Efficient Bifunctional Electrocatalyst for Alkaline Water Electrolysis","authors":"Vidhi Agarwal, Bidyut Chutia, Ravindra Vishwakarma, Aditya Prasun, Amrita Chakraborty, Sasanka Deka, Tridib K Sarma","doi":"10.1002/smll.202512303","DOIUrl":"https://doi.org/10.1002/smll.202512303","url":null,"abstract":"Amid the global drive to eliminate carbon emissions and to mitigate the energy crisis, water splitting emerges as a beacon of innovation, converting water into clean hydrogen and oxygen. Most electrocatalysts for water splitting rely on precious metals, highlighting the demand for cost-effective, efficient, and reproducible alternatives. Herein, we report the development of a cobalt-adenosine monophosphate (CAH) hydrogel as a bifunctional catalyst for overall water splitting in alkaline conditions with a cell voltage of 1.56 V at 10 mA cm<sup>−2</sup>, outperforming the benchmark catalytic system IrO<sub>2</sub>||Pt/C (1.62 V at 10 mA cm<sup>−2</sup>). Three crucial factors contributed to the notable water splitting of this hydrogel: (i) phosphate group in the AMP coordinated with central Co<sup>2+</sup> ions, promoting effective adsorption of key intermediates, (ii) tetrahedral arrangement around cobalt atoms making the active site more exposed and accessible, enabling better interaction with reactants and intermediates, (iii) the formation of hydrogel enhances electrolyte confinement, thus accelerating reaction kinetics. At elevated temperature, the hydrogel achieves a low cell voltage of 1.42 V at 1.0 M KOH. Even under industrially relevant harsh conditions, the hydrogel achieves 10 mA cm<sup>−2</sup> at 1.53 V, underscoring its durability. This simple nucleotide-based coordination polymer might bring significant advancement in sustainable energy conversion.","PeriodicalId":228,"journal":{"name":"Small","volume":"69 1","pages":""},"PeriodicalIF":13.3,"publicationDate":"2026-02-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146122473","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Solvent-Regulated CPL Enhancement via Chiral Transfer in Efficient Luminescent Ionic Hydrogen-Bonded Frameworks for Information Encryption 通过手性转移在高效发光离子氢键框架中的溶剂调节CPL增强,用于信息加密
IF 13.3 2区 材料科学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2026-02-06 DOI: 10.1002/smll.202513678
Bin Zhou, Li-Hui Cao, Yi Yang, Dan Zhao, Chen-Yang Liu, Xiao-Jie Cao
Circularly polarized luminescence (CPL) materials have garnered significant attention due to their broad application prospects in information-encryption and optical storage. However, chiral small-molecule systems face challenges such as intramolecular chiral-transfer confinement and low energy transfer efficiency, making it difficult to achieve breakthroughs in chiral optical properties using a single component. We propose a multistage chiral-transfer-strategy based on ionic hydrogen-bonded organic frameworks (iHOFs), utilizing (1R/1S,2R/2S)-1, 2-diphenylethylenediamine-(R/S-DPEN) as the chiral source and 4,4′-bis(2-sulfonatostyryl)biphenyl-(H2CBS) as the chromophore to synthesize R/S-iHOF-40. Our study reveals that the introduction of an effective charge donor modulates the excited-state energy gap, which is the primary reason for R/S-iHOF-40’s high quantum yield (QY) of 67.8% (compared to 5.41% for HOF-R/S-DPEN). Furthermore, the strong mirror cotton effect observed at 323 nm for R/S-iHOF-40 confirms effective intermolecular chiral-transfer, while the crystal structure clearly reveals a double-helix supramolecular assembly mechanism mediated by hydrogen-bond bridging. Interestingly, the interference of water molecule motion within the structure on the chiral coupling between ions demonstrates the crucial role of hydrogen-bond dynamics in regulating the chiral emission of the R/S-iHOF-40 excited state. This work deepens our understanding of the mechanisms of chiral-transfer and amplification, and provides new strategies for the application of solid-state chiral materials in information-encryption.
圆偏振发光材料在信息加密和光存储等方面具有广阔的应用前景,引起了人们的广泛关注。然而,手性小分子体系面临着分子内手性转移限制和低能量转移效率等挑战,使得单组分手性光学性质难以实现突破。本文提出了一种基于离子氢键有机骨架(iHOFs)的多阶段手性转移策略,以(1R/1S,2R/2S)- 1,2 -二苯乙二胺-(R/S-DPEN)为手性源,4,4′-双(2-磺酰基苯基)联苯-(H2CBS)为发色团合成R/ s - iHOFs -40。我们的研究表明,有效电荷供体的引入调节了激发态能隙,这是R/S-iHOF-40的高量子产率(QY)达到67.8%(而HOF-R/S-DPEN为5.41%)的主要原因。此外,在323 nm处观察到的R/S-iHOF-40的强镜像棉效应证实了有效的分子间手性转移,而晶体结构清楚地揭示了氢键桥接介导的双螺旋超分子组装机制。有趣的是,结构内水分子运动对离子间手性偶联的干扰证明了氢键动力学在调节R/S-iHOF-40激发态手性发射中的关键作用。这项工作加深了我们对手性转移和放大机制的理解,并为固态手性材料在信息加密中的应用提供了新的策略。
{"title":"Solvent-Regulated CPL Enhancement via Chiral Transfer in Efficient Luminescent Ionic Hydrogen-Bonded Frameworks for Information Encryption","authors":"Bin Zhou, Li-Hui Cao, Yi Yang, Dan Zhao, Chen-Yang Liu, Xiao-Jie Cao","doi":"10.1002/smll.202513678","DOIUrl":"https://doi.org/10.1002/smll.202513678","url":null,"abstract":"Circularly polarized luminescence (CPL) materials have garnered significant attention due to their broad application prospects in information-encryption and optical storage. However, chiral small-molecule systems face challenges such as intramolecular chiral-transfer confinement and low energy transfer efficiency, making it difficult to achieve breakthroughs in chiral optical properties using a single component. We propose a multistage chiral-transfer-strategy based on ionic hydrogen-bonded organic frameworks (iHOFs), utilizing (1R/1S,2R/2S)-1, 2-diphenylethylenediamine-(R/S-DPEN) as the chiral source and 4,4′-bis(2-sulfonatostyryl)biphenyl-(H<sub>2</sub>CBS) as the chromophore to synthesize <b>R/S-iHOF-40</b>. Our study reveals that the introduction of an effective charge donor modulates the excited-state energy gap, which is the primary reason for <b>R/S-iHOF-40</b>’s high quantum yield (QY) of 67.8% (compared to 5.41% for HOF-R/S-DPEN). Furthermore, the strong mirror cotton effect observed at 323 nm for <b>R/S-iHOF-40</b> confirms effective intermolecular chiral-transfer, while the crystal structure clearly reveals a double-helix supramolecular assembly mechanism mediated by hydrogen-bond bridging. Interestingly, the interference of water molecule motion within the structure on the chiral coupling between ions demonstrates the crucial role of hydrogen-bond dynamics in regulating the chiral emission of the <b>R/S-iHOF-40</b> excited state. This work deepens our understanding of the mechanisms of chiral-transfer and amplification, and provides new strategies for the application of solid-state chiral materials in information-encryption.","PeriodicalId":228,"journal":{"name":"Small","volume":"9 1","pages":""},"PeriodicalIF":13.3,"publicationDate":"2026-02-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146122472","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
The Chemistry From Tin Iodide Molecular Inks to FASnI3 Nanocrystals. 从碘化锡分子墨水到FASnI3纳米晶体的化学性质。
IF 12.1 2区 材料科学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2026-02-06 DOI: 10.1002/smll.202511842
Kushagra Gahlot, Julia N Kraft, Manuel Pérez-Escribano, Mihai T Todosia, Karla Ravin, Joaquín Calbo, Loredana Protesescu

The controlled synthesis of high-performance tin halide perovskite nanostructures hinges on the coordination chemistry that governs precursor speciation within molecular inks. Here, we elucidate the complexation dynamics of SnI2 with two benchmark Lewis bases widely used in nanocrystal syntheses: a strong primary amine (R-NH2) and a weaker substituted phosphine (R'3-P). Correlated in situ 1 1 9Sn NMR and UV-Vis absorption spectroscopy, supported by density functional theory calculations, reveal that both ligands (L) form monomeric SnI2-L adducts, with R-NH2 consistently exhibiting stronger coordination than R3'-P, as quantified by the intrinsic bond strength index and interaction energies. Higher ligand loadings destabilize SnI2-Lx complexes, particularly for phosphines, whereas we show that amine-bound multimeric (SnI2)x(R-NH2)x (x = 2-3) species can be present at low ligand concentrations. These molecular-level insights directly correlate with nanocrystal formation pathways. Stronger Sn─N coordination drives the emergence of 2D Ruddlesden-Popper phases, while weaker Sn-P interactions favor bulk-like 3D FASnI3 nanocrystals due to insufficient stabilization of early-stage intermediates. Guided by this understanding, an amine-free, three-precursor strategy employing a strong zwitterionic ligand enables phase-pure 3D FASnI3 nanocrystals with improved optical and colloidal stability. This work establishes a predictive framework for designing robust molecular inks for tin halide perovskites and perovskitoid nanostructures.

高性能卤化锡钙钛矿纳米结构的受控合成取决于控制分子油墨中前驱体形态的配位化学。在这里,我们阐明了SnI2与两种广泛用于纳米晶体合成的基准路易斯碱的络合动力学:强伯胺(R- nh2)和弱取代膦(R'3-P)。在密度泛函理论计算的支持下,现场核磁共振和紫外-可见吸收光谱结果表明,两种配体(L)形成了单体SnI2-L加合物,其中R-NH2的配位性一直比R3'-P强,这是由内在键强度指数和相互作用能量化的。较高的配体负荷会破坏SnI2- lx配合物的稳定性,特别是对于膦,而我们发现胺结合的多聚体(SnI2)x(R-NH2)x (x = 2-3)可以在低配体浓度下存在。这些分子水平的见解与纳米晶体的形成途径直接相关。较强的Sn─N配位驱动2D Ruddlesden-Popper相的出现,而较弱的Sn─p相互作用由于早期中间体稳定性不足而有利于块状3D FASnI3纳米晶体的形成。在这种理解的指导下,采用强两性离子配体的无胺三前体策略使相纯3D FASnI3纳米晶体具有更好的光学和胶体稳定性。这项工作为设计卤化锡钙钛矿和类钙钛矿纳米结构的坚固分子墨水建立了预测框架。
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引用次数: 0
Electronic Structure Modulation via Composition-Preserving Phase Transformations in Metal–Organic Assemblies on the Surface 表面金属有机组件中保持成分相变的电子结构调制
IF 13.3 2区 材料科学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2026-02-06 DOI: 10.1002/smll.202513441
Hyungjun Park, Emiko Kazuma, Minhui Lee, Sylvain Clair, Jaehoon Jung, Yousoo Kim
Supramolecular self-assemblies based on metal–organic coordination provide a tunable platform for constructing functional nanostructures on surfaces, with potential applications in catalysis, magnetism, and optoelectronics. Rational design of assemblies requires understanding how their electronic structures can be tuned by various factors, such as precursor design and substrate choice. While phase transformations can significantly alter both structural and electronic properties, most reported cases involve changes in chemical composition or bonding configurations. In contrast, systematic studies of geometric relaxation, which is modulated without altering chemical identity, remain limited, as such transformations often demand high temperatures that risk side reactions. In this study, we demonstrate a room-temperature phase transformation in a supramolecular self-assembly of Ag–carboxylate complexes derived from 3,5-dinitrobenzoic acid on Ag(111), proceeding without any changes in chemical composition. Combining scanning tunneling microscopy and spectroscopy with density functional theory calculations, we track a stepwise transformation among three distinct hexagonal lattices. The transformation induces subtle geometric relaxation that strengthens metal–molecule interactions, thereby modulating the collective electronic structure. Unlike previous studies on polymorphic organic assemblies, this work reveals a composition-preserving, phase-transformation-driven route to modulate electronic structures in metal–organic coordination assemblies, enabling tuning of physicochemical functionalities in surface-confined molecular architectures.
基于金属-有机配位的超分子自组装为在表面上构建功能纳米结构提供了一个可调的平台,在催化、磁性和光电子学方面具有潜在的应用前景。组件的合理设计需要了解如何通过各种因素调整其电子结构,例如前驱体设计和衬底选择。虽然相变可以显著改变结构和电子性质,但大多数报道的情况涉及化学成分或键构型的变化。相比之下,对几何弛豫的系统研究,在不改变化学特性的情况下进行调制,仍然有限,因为这种转变通常需要高温,有可能产生副反应。在这项研究中,我们证明了由3,5-二硝基苯甲酸衍生的Ag -羧酸配合物在Ag(111)上的超分子自组装在室温下发生相变,而化学成分没有任何变化。结合扫描隧道显微镜和光谱学以及密度泛函理论计算,我们跟踪了三个不同的六边形晶格之间的逐步变换。这种转变引起了微妙的几何弛豫,从而加强了金属分子之间的相互作用,从而调节了集体电子结构。与以往对多晶有机组装体的研究不同,这项工作揭示了一种成分保持、相变驱动的方法来调制金属有机配位组装体中的电子结构,从而可以调节表面受限分子结构中的物理化学功能。
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引用次数: 0
Graphene Oxide Nanosheets as Direct Photosensitizers for Photodynamic Therapy in a Size-Dependent Manner 氧化石墨烯纳米片作为光动力治疗的直接光敏剂
IF 13.3 2区 材料科学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2026-02-06 DOI: 10.1002/smll.202513685
Chenhao Yu, Shangyan Sui, Xiaotong Yu, Qianming Chen, Qiang Peng
Photodynamic therapy (PDT) has shown great potential in anticancer treatment. Photosensitizer is a key element determining the efficiency of PDT, but its practical use is highly limited by some critical problems, such as low photostability and poor solubility. As such, developing novel photosensitizers is of great significance and importance for PDT. In this work, we report the size-dependent photodynamic effect of graphene oxide (GO) nanosheets, which are commonly used as carriers for drug delivery. GO (200 µg/mL) with a large size up to ∼3500 nm showed little cytotoxicity to HSC-3 cells (oral squamous cell carcinoma cell line) but caused the cell viability down to 8% under NIR irradiation due to the robust generation of intracellular reactive oxygen species (ROS). Large GO-induced ROS generation is also significant even under hypoxia. Animal study shows that large GO even induced tumor ablation directly under a single NIR irradiation. Our findings indicate that GO is much more than a carrier but can also be a great photosensitizer when its size is large enough. This work paves the way for the potential applications of GO as the photosensitizer in PDT.
光动力疗法(PDT)在抗癌治疗中显示出巨大的潜力。光敏剂是决定PDT效率的关键因素,但由于光稳定性差、溶解性差等关键问题,光敏剂的实际应用受到很大限制。因此,开发新型光敏剂对PDT具有重要的意义和意义。在这项工作中,我们报告了氧化石墨烯(GO)纳米片的尺寸依赖性光动力学效应,氧化石墨烯通常被用作药物递送的载体。大尺寸氧化石墨烯(200µg/mL)可达~ 3500 nm,对HSC-3细胞(口腔鳞状细胞癌细胞系)几乎没有细胞毒性,但由于细胞内活性氧(ROS)的强劲生成,在近红外照射下使细胞活力下降到8%。即使在缺氧情况下,大量氧化石墨烯诱导的ROS生成也很明显。动物研究表明,在单次近红外照射下,大氧化石墨烯甚至直接诱导肿瘤消融。我们的研究结果表明,氧化石墨烯不仅仅是一种载体,当它的尺寸足够大时,它也可以是一种很好的光敏剂。这项工作为氧化石墨烯作为光敏剂在PDT中的潜在应用铺平了道路。
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引用次数: 0
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